CN114538899B - Preparation method of 996 aluminum oxide ceramic substrate - Google Patents
Preparation method of 996 aluminum oxide ceramic substrate Download PDFInfo
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- CN114538899B CN114538899B CN202210070334.0A CN202210070334A CN114538899B CN 114538899 B CN114538899 B CN 114538899B CN 202210070334 A CN202210070334 A CN 202210070334A CN 114538899 B CN114538899 B CN 114538899B
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B17/00—Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
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Abstract
The invention relates to the technical field of ceramic substrates, and provides a preparation method of a 996 aluminum oxide ceramic substrate, which comprises the following steps: (1) preparing a sintering aid; (2) preparing slurry; (3) tape casting and stamping; (4) removing glue; and (5) sintering. The invention optimizes the formula and the process of the alumina ceramic, increases the content of the alumina to 99.6 percent, and reduces the sintering temperature while improving the electrical property and the mechanical property of the alumina ceramic. Solves the problems of poor quality stability and overhigh sintering temperature of the 99 porcelain products produced by the prior art.
Description
Technical Field
The invention relates to the technical field of ceramic substrates, in particular to a preparation method of a 996 aluminum oxide ceramic substrate.
Background
With the continuous development of the packaging technology in the electronic industry, research and development progress is gradually made in the directions of high integration level, complete functions, excellent performance and strong reliability. The substrate material mainly plays roles of insulation, heat dissipation, protection, chip bearing, metal electronic circuit bearing and the like in the electronic packaging process. Compared with other electronic substrate materials, the aluminum oxide ceramic material has the characteristics of high hardness, good chemical corrosion resistance, high bending strength, good expansion coefficient matching property and the like, is rich in raw materials and low in price, and becomes a ceramic substrate material with the largest application amount and the widest application field. The application field of the device mainly comprises electronic and microelectronic products such as electronic ceramic elements, chip resistors, ceramic copper-clad plates, LED radiating fins, focusing potentiometers, ozone generators, sensor insulating lining plates and the like.
In practical applications, the alumina content of the ceramics higher than 75% is called alumina ceramics. Alumina ceramics are generally classified according to the content of alumina, for example, alumina ceramics with a content of about 75%, 90%, 95%, 99% are respectively referred to as 75 porcelain, 90 porcelain, 95 porcelain, and 99 porcelain. The 99 porcelain has the advantages of good mechanical property, low dielectric constant, small dielectric loss, stable electrical property and the like, so that the 99 porcelain is often applied to the high-tech field and the military field with harsh working environment. However, the 99 porcelain produced by the prior art has poor quality stability, and the sintering porcelain forming temperature is too high during production, thereby seriously hindering the further development of the product.
An invention patent CN112174648A published in 2021, 1 and 5 discloses a preparation method of a high-purity alumina ceramic substrate, which comprises the following steps: s1, putting 99-99.5 parts by weight of high-purity alumina powder and 0.5-1 part by weight of sintering aid into a ball mill, adding water as a solvent and a water-soluble dispersant, and grinding and mixing to obtain slurry; s2, removing bubbles of the slurry in vacuum, feeding the slurry into a slurry barrel, adding a catalyst and an initiator, uniformly stirring, connecting with an air source, starting the air source to apply pressure to the slurry to control the slurry to be injected into the mold from a slurry injection port at the bottom of the mold through a communicating pipe, enabling the slurry to flow in the mold from bottom to top until the mold is filled, and curing and demolding to obtain a green body; s3, drying the blank body, softening, cutting into blank sheets and drying; and S4, sintering the blank sheet, and flattening to obtain the substrate. The substrate has the advantages of low sintering temperature, wide sintering range and controllable sintering shrinkage. The gas source is used for applying pressure to the slurry, so that the slurry is injected into the mold from bottom to top, and the problems of large density difference and large molding defect of a green body caused by the deposition of materials with high specific gravity in the slurry to the bottom of the mold are solved.
The invention optimizes the formula and the process of the alumina ceramic, increases the content of the alumina to 99.6 percent, improves the electrical property and the mechanical property of the alumina ceramic and reduces the production cost at the same time.
Disclosure of Invention
Therefore, aiming at the content, the invention provides a preparation method of a 996 alumina ceramic substrate, which solves the problems that the quality stability of the 99 ceramic product produced by the prior art is poor and the temperature of the sintered ceramic is overhigh.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a 996 aluminum oxide ceramic substrate comprises the following steps:
(1) Sintering aidThe preparation of (1): adding copper nitrate, titanium glycerol, tetraethoxysilane, acrylic acid, a polyethylenimine cross-linking agent, sodium tripolyphosphate and ethanol into a reactor filled with water in proportion, stirring for 30-60 min at the temperature of 60-70 ℃, then adding a free radical initiator, stirring for reaction until gel is formed, standing for 20-30 h at room temperature, then dehydrating and drying, grinding to obtain powder, then putting the powder into a calcining furnace for calcining to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid;
(2) Preparation of slurry: adding alumina powder and a sintering aid into a ball mill according to a mass ratio of 99.6 to 0.4, simultaneously adding a solvent, a dispersing agent, a bonding agent and a defoaming agent into the ball mill, ball-milling for 15-20 h, and then feeding into a defoaming device for defoaming treatment to obtain slurry with good and stable fluidity;
the defoaming device comprises a defoaming tank and a vacuum pump, wherein a feed inlet and an air exhaust port are respectively arranged on two sides of the top of the defoaming tank, the air exhaust port is communicated with the vacuum pump through a vacuum tube, a driving motor is mounted on the top of the defoaming tank, the output end of the driving motor is fixedly connected with a rotating shaft, the bottom end of the rotating shaft penetrates through the top of the defoaming tank and is hinged with the top end of a stirring shaft, the stirring shaft is fixedly connected with the inner wall of the bottom of the defoaming tank through a bearing, the stirring shaft is fixedly connected with a plurality of first stirring units and second stirring units, the first stirring units and the second stirring units are alternately arranged along the length direction of the stirring shaft, the first stirring units comprise 3-6 stirring rods, the second stirring units comprise 2-4 stirring blades, the stirring rods and the outer walls of the stirring blades are fixedly connected with foam breaking burrs, the stirring rods comprise longitudinal stirring rods and transverse stirring rods, the longitudinal stirring rods and the transverse stirring rods are fixedly connected, a discharge port is arranged at the bottom of the side wall of the defoaming tank, and the discharge port is connected with a discharge pipe;
(3) Tape casting and stamping: treating the slurry by a casting machine and a sheet punching machine to obtain a green compact sheet with a required shape and size;
(4) Rubber discharging: placing the green sheet into a glue discharging furnace for glue discharging;
(5) And (3) sintering: and placing the green blank sheet after the glue discharging into a sintering furnace, heating to 1500 ℃ at the speed of 1.5-2.5 ℃/min, preserving the heat for 10-20 min, cooling to 1450 ℃, preserving the heat for 12-20 h, cooling and taking out to obtain the 996 aluminum oxide ceramic substrate.
The further improvement is that: the water in the step (1) accounts for 100% by mass, and the addition amount of each raw material component is as follows: 7 to 9 percent of copper nitrate, 16 to 20 percent of titanium glycerol, 36 to 42 percent of tetraethoxysilane, 8 to 12 percent of acrylic acid, 1 to 3 percent of polyethylenimine cross-linking agent, 0.2 to 0.4 percent of sodium tripolyphosphate, 8 to 15 percent of ethanol and 0.4 to 0.8 percent of free radical initiator.
The further improvement is that: the free radical initiator is persulfate initiator.
The further improvement is that: the calcination temperature in the step (1) is 620-660 ℃.
The further improvement is that: the alumina powder is prepared by mixing alpha-phase alumina with the average grain size of 3-5 mu m and alpha-phase alumina with the average grain size of 50nm according to the mass ratio of 20-40.
The further improvement is that: the dispersant is prepared by compounding polyethyleneimine and sodium alkyl benzene sulfonate according to the mass ratio of 1:1-4:1.
The further improvement is that: be equipped with deaeration portion between the discharging pipe, deaeration portion includes spherical shell and the dwang of setting in spherical shell, the vertical direction setting of dwang, the dwang outer wall has cup jointed the defoaming ball, be equipped with broken bubble thorn on the defoaming ball, when the dwang rotates under the drive arrangement effect, the drive takes off the bubble ball and rotates, eliminates remaining bubble in the thick liquids.
The further improvement is that: the side wall of the defoaming tank is provided with a heating pipe, the heating pipe surrounds the defoaming tank, and the inner wall of the defoaming tank is provided with a temperature sensor.
The further improvement is that: the addition amounts of the solvent, the dispersant, the adhesive and the defoaming agent are 180-220%, 3.5-5.5%, 10-15% and 0.9-1.6% in sequence based on 100% of the mass of the alumina powder.
The further improvement is that: the concrete process parameters of the glue discharging in the step (4) are as follows: performing first glue removal in a nitrogen atmosphere, heating to 500-580 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 30-50 min, then performing second glue removal in an air atmosphere, heating to 210-240 ℃ at a heating rate of 2-4 ℃/min, and preserving heat for 100-150 min.
By adopting the technical scheme, the invention has the beneficial effects that:
the copper oxide forms a liquid phase in the sintering process to promote the densification of the alumina ceramic; formation of Al from titanium dioxide and alumina 2 Ti 7 O 15 Simultaneously forming a large number of positive ion vacancies so as to promote the growth of crystal grains and the densification process of the alumina ceramics; the silicon dioxide can generate a glass phase in the sintering process and can form a low-temperature eutectic body with the aluminum oxide to play a role in promoting sintering. Copper oxide, titanium dioxide and silicon dioxide are compounded to form a ternary sintering aid system, so that sintering can be better promoted, the sintering temperature is reduced, and the comprehensive performance of the alumina ceramic can be improved. The existing multi-element sintering aid is prepared by putting various sintering aids into a ball milling tank for ball milling, grinding and sieving, theoretically, enough liquid phase can be formed in the sintering process, so that the aluminum oxide particles can generate a lubricating effect, the migration and rearrangement of the particles are facilitated, and the tissues in a blank body are more uniform; meanwhile, the liquid phase can also be filled into the gaps among the alumina particles to eliminate air holes, thereby improving the density of the green body. The applicant finds that the components of the multi-element sintering aid prepared by the traditional method are not uniformly dispersed and are easy to agglomerate, a small amount of liquid phase is formed at high temperature, the particles are difficult to lubricate, the liquid phase is difficult to fill in the pores among the particles, the pores are difficult to eliminate and remain, and the compactness of the alumina ceramic is finally influenced. The applicant adopts the CuO-TiO obtained by the new preparation method 2 -SiO 2 The ternary sintering aid is uniformly dispersed, and improves aggregation and reunion among powder, and the specific principle is as follows: firstly, acrylic acid is subjected to free radical polymerization reaction to form a polymer, and then the polymer and a polyethylenimine crosslinking agent are subjected to crosslinking reaction to form a three-dimensional reticular skeleton structure, and the structure can generate a space blocking and shielding effect, effectively inhibit the occurrence of an agglomeration phenomenon and improve the dispersibility. Secondly, sodium tripolyphosphate is inA large number of ionic groups are ionized in water and adsorbed on the surfaces of gel particles, so that the charge quantity on the surfaces of the particles is increased, and the distance between the particles is increased by utilizing the principle that like poles repel each other; in addition, the sodium tripolyphosphate can also form molecular chains on the particle surface to play a role of steric hindrance, so that agglomeration is further prevented. Finally, organic matters in the gel are removed through calcination to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid. More liquid phases are generated in the sintering process, so that the density and the mechanical property of the produced alumina ceramic are higher than those of the alumina ceramic prepared by adding the ternary sintering aid of the traditional process.
The sintering temperature of the high-purity alumina ceramic is usually higher than 1700 ℃, the sintering temperature can be reduced by adding the sintering aid, and MgO-SiO is commonly used at home at present 2 -Al 2 O 3 And CaO-MgO-SiO 2 -Al 2 O 3 The alumina ceramic prepared by the sintering aid system has good mechanical property and electrical property, but the sintering temperature is still higher than 1580 ℃, and the production cost is high. In this regard, the applicant has improved from several aspects: first aspect, cuO-TiO produced by a novel preparation Process 2 -SiO 2 The ternary sintering aid can better promote sintering and reduce sintering temperature. In the second aspect, micron-sized and nano-sized aluminum oxide particles are compounded, so that the surface activity of the nano-sized aluminum oxide particles is high, and the sintering temperature is obviously reduced; meanwhile, the nano-scale particles can be filled into gaps of the micro-scale particles and are tightly stacked, so that the alumina factory ceramic product with high density is obtained. The nano alumina particles are easy to generate agglomeration, so that the sintered ceramic grains are not uniform, and the comprehensive performance of the product is influenced. The composite system of polyethyleneimine and sodium alkyl benzene sulfonate is effectively adsorbed on the surface of nano alumina particles, so that the formation of agglomerated macromolecules is reduced. In the third aspect, different from the prior art that the temperature is directly raised to the highest temperature and is subjected to long-time heat preservation sintering at the highest temperature, the method adopts a sectional sintering mode, firstly, the temperature is raised to 1500 ℃, the green body achieves certain densification, then, the temperature is lowered to 1450 ℃, the green body is nearly completely densified through low-temperature grain boundary diffusion, and the problem of large energy is avoidedThe amount is wasted, and the cost is reduced. Meanwhile, the crystal boundary migration is inhibited, and the growth of the crystal grains of the blank is inhibited, so that the mechanical property of the alumina ceramic is improved.
The existing defoaming device has unreasonable structural design and poor defoaming efficiency, and is difficult to completely eliminate the foaming in the slurry, so that the sequential proceeding of the subsequent processes is influenced, and the produced alumina ceramic substrate has defects. This application adopts modified deaeration device, through mutually supporting of vacuum pump, driving motor, first stirring unit, second stirring unit and broken bubble thorn, has reached good deaeration effect. The stirring blades are divided into a longitudinal stirring rod and a transverse stirring rod, so that the stirring coverage is improved, dead corners are avoided, and bubbles in the slurry are fully removed. The slurry in the de-foaming tank is properly heated by the heating pipe, so that the flowing speed of the slurry is increased, bubbles can quickly escape from the slurry, and the de-foaming efficiency is improved. The defoaming effect can be further guaranteed through the arrangement of the defoaming portion, if bubbles which are not completely eliminated are remained in the slurry, bubble breaking burrs on the defoaming ball and the residual bubbles are punctured in the contact process of the slurry, and smooth proceeding of the subsequent processing process is guaranteed.
Drawings
FIG. 1 is a schematic structural diagram of a defoaming apparatus in an embodiment of the present invention;
fig. 2 is an enlarged schematic view of a in fig. 1.
Detailed Description
The following detailed description will be given with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagent used are indicated at the first appearance.
Example 1
A preparation method of a 996 aluminum oxide ceramic substrate comprises the following steps:
(1) Preparing a sintering aid: adding copper nitrate, titanium glycerol, tetraethoxysilane, acrylic acid, a polyethylenimine cross-linking agent, sodium tripolyphosphate and ethanol into a reactor filled with water in proportion, stirring for 30min at 60 ℃, then adding ammonium persulfate, stirring for reaction to form gel, standing for 20h at room temperature, then dehydrating and drying, grinding to obtain powder, then putting the powder into a calcining furnace for calcining at 620 ℃ to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid;
the additive amount of each raw material component is as follows according to the mass of water 100 percent: 7% of copper nitrate, 16% of titanium glycerol, 36% of tetraethoxysilane, 8% of acrylic acid, 1% of polyethylenimine crosslinking agent, 0.2% of sodium tripolyphosphate, 8% of ethanol and 0.4% of ammonium persulfate;
(2) Preparation of slurry: adding alumina powder and a sintering aid into a ball mill according to a mass ratio of 99.6.4, simultaneously adding isopropanol, a dispersing agent, a bonding agent and a defoaming agent into the ball mill, ball-milling for 15 hours, and then sending into a defoaming device for defoaming treatment to obtain slurry with good and stable fluidity;
the alumina powder is prepared by mixing alpha-phase alumina (produced by catalpo macro-Hao crystal materials, inc.) with the average grain size of 3-5 mu m and alpha-phase alumina (produced by Hangzhou Cudrania tricuspidata new materials, inc., the model is ZM-AL 50) with the average grain size of 50nm according to the mass ratio of 20 to 80, the dispersing agent is prepared by compounding polyethylene imine and sodium alkyl benzene sulfonate according to the mass ratio of 1:1, the adhesive is polyvinyl butyral, and the addition amounts of isopropanol, the dispersing agent, the adhesive and the defoaming agent are 180%, 3.5%, 10% and 0.9% in sequence by taking 100% of the mass of the alumina powder;
referring to fig. 1 and 2, the defoaming device comprises a defoaming tank 1 and a vacuum pump 2, wherein a feed inlet 3 and an extraction opening 4 are respectively arranged on two sides of the top of the defoaming tank, the air exhaust port 4 is communicated with the vacuum pump 2 through a vacuum tube, the top of the defoaming tank 1 is provided with a driving motor 5, the output end of the driving motor 5 is fixedly connected with a rotating shaft 6 through a coupler, the bottom end of the rotating shaft 6 penetrates through the top of the deaeration tank 1 and is hinged with the top end of a stirring shaft 7, the stirring shaft 7 is fixedly connected with the inner wall of the bottom of the deaeration tank 1 through a bearing, the stirring shaft 7 is fixedly connected with a plurality of first stirring units and second stirring units, the first stirring unit and the second stirring unit are alternately arranged along the length direction of the stirring shaft 7, the first stirring unit consists of 5 stirring rods 8 which are distributed at equal intervals, the second stirring unit consists of 3 stirring blades 9 which are distributed at equal intervals, the outer walls of the stirring rod 8 and the stirring blades 9 are fixedly connected with bubble breaking thorns 10, the stirring rod 8 comprises a longitudinal stirring rod 81 and a transverse stirring rod 82, the longitudinal stirring rod 91 is fixedly connected with the transverse stirring rod 92, a heating pipe 11 is arranged on the side wall of the defoaming tank 1, the heating pipe 11 is surrounded on the defoaming tank 1, a temperature sensor 12 for detecting the real-time temperature of the slurry is arranged on the inner wall of the deaeration tank 1, a discharge hole 13 is arranged at the bottom of the side wall of the deaeration tank 1, the discharge port 13 is connected with a discharge pipe 14, a defoaming part is arranged between the discharge pipes 14, the defoaming part comprises a spherical shell 15 and a rotating rod 16 arranged in the spherical shell, the rotating rod is arranged in the vertical direction, the outer wall of the rotating rod 16 is sleeved with a defoaming ball 17, and defoaming thorns are arranged on the defoaming ball 17;
during operation, the slurry is guided into the defoaming tank through the feeding port, then the defoaming tank is closed and sealed, the driving motor is started, the rotating shaft starts to rotate, the stirring shaft is driven to rotate, the first stirring unit and the second stirring unit which are connected with the stirring shaft stir the slurry, the vacuum pump is started simultaneously, gas in the defoaming tank is pumped out, negative pressure is formed in the vacuum tank, and slurry bubbles continuously escape under the action of the negative pressure after stirring. The heating pipe and the temperature sensor are mutually matched, so that the slurry is at a proper temperature, and bubbles are easier to escape from the slurry. When the slurry flows out of the discharge hole, the rotating rod drives the defoaming balls to rotate under the action of the driving device, so that bubbles remained in the slurry are eliminated;
(3) Tape casting and stamping: treating the slurry by a casting machine and a sheet punching machine to obtain a green compact sheet with a required shape and size;
(4) Rubber discharging: putting the green body sheet into a glue discharging furnace for discharging glue, wherein the specific technological parameters are as follows: performing first glue removal in a nitrogen atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, preserving heat for 50min, performing second glue removal in an air atmosphere, heating to 210 ℃ at a heating rate of 2 ℃/min, and preserving heat for 150min;
(5) And (3) sintering: and (3) placing the green blank sheet after the glue removal into a sintering furnace, heating to 1500 ℃ at the speed of 1.5 ℃/min, preserving heat for 10min, cooling to 1450 ℃, preserving heat for 12h, cooling and taking out to obtain the 996 aluminum oxide ceramic substrate.
The alumina ceramic substrate prepared in this example was tested and had the following properties: the relative density is 98.0 percent, and the volume density is 3.90g/cm 3 The bending strength is 485MPa.
Example 2
A preparation method of a 996 aluminum oxide ceramic substrate comprises the following steps:
(1) Preparing a sintering aid: adding copper nitrate, titanium glycerol, tetraethoxysilane, acrylic acid, a polyethylenimine cross-linking agent, sodium tripolyphosphate and ethanol into a reactor filled with water in proportion, stirring for 45min at 65 ℃, then adding potassium persulfate, stirring for reaction to form gel, standing for 25h at room temperature, dehydrating, drying, grinding to obtain powder, then putting the powder into a calcining furnace for calcining at 640 ℃ to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid;
the additive amount of each raw material component is as follows according to the mass of water 100 percent: 8% of copper nitrate, 18% of titanium glycerol, 40% of tetraethoxysilane, 10% of acrylic acid, 2% of polyethylenimine crosslinking agent, 0.3% of sodium tripolyphosphate, 12% of ethanol and 0.6% of potassium persulfate;
(2) Preparation of slurry: adding alumina powder and a sintering aid into a ball mill according to a mass ratio of 99.6.4, simultaneously adding isopropanol, a dispersing agent, a bonding agent and a defoaming agent into the ball mill, carrying out ball milling for 18 hours, and then sending into a defoaming device for defoaming treatment to obtain slurry with good and stable fluidity;
the alumina powder is formed by mixing alpha-phase alumina with the average grain diameter of 3-5 mu m and alpha-phase alumina with the average grain diameter of 50nm according to the mass ratio of 30 to 70, the dispersant is formed by compounding polyethyleneimine and sodium alkyl benzene sulfonate according to the mass ratio of 2:1,
the addition amounts of the isopropanol, the dispersant, the adhesive and the defoaming agent are 200%, 4.5%, 12% and 1.2% in sequence based on 100% of the mass of the alumina powder;
(3) Tape casting and stamping: treating the slurry by a casting machine and a sheet punching machine to obtain a green compact sheet with a required shape and size;
(4) Rubber discharging: putting the green body sheet into a glue discharging furnace for discharging glue, wherein the specific technological parameters are as follows: performing first glue discharging in nitrogen atmosphere, heating to 550 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 40min, performing second glue discharging in air atmosphere, heating to 230 ℃ at a heating rate of 3 ℃/min, and preserving heat for 120min;
(5) And (3) sintering: and (3) placing the green blank sheet after the glue removal into a sintering furnace, heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 15min, cooling to 1450 ℃, preserving heat for 16h, cooling and taking out to obtain the 996 aluminum oxide ceramic substrate.
The alumina ceramic substrate prepared in this example was tested and had the following properties: the relative density is 99.2 percent, and the volume density is 3.99g/cm 3 The flexural strength was 522MPa.
Example 3
A preparation method of a 996 aluminum oxide ceramic substrate comprises the following steps:
(1) Preparing a sintering aid: adding copper nitrate, titanium glycerol, tetraethoxysilane, acrylic acid, a polyethylenimine cross-linking agent, sodium tripolyphosphate and ethanol into a reactor filled with water in proportion, stirring for 60min at 70 ℃, then adding ammonium persulfate, stirring for reaction to form gel, standing for 30h at room temperature, then dehydrating and drying, grinding to obtain powder, then putting the powder into a calcining furnace for calcining at 660 ℃ to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid;
the additive amount of each raw material component is as follows according to 100% of the mass of water: 9% of copper nitrate, 20% of titanium glycerol, 42% of tetraethoxysilane, 12% of acrylic acid, 3% of polyethylenimine crosslinking agent, 0.4% of sodium tripolyphosphate, 15% of ethanol and 0.8% of ammonium persulfate;
(2) Preparing slurry: adding alumina powder and a sintering aid into a ball mill according to a mass ratio of 99.6 to 0.4, simultaneously adding a solvent, a dispersing agent, a bonding agent and a defoaming agent into the ball mill, carrying out ball milling for 20 hours, and then sending the mixture into a defoaming device for defoaming treatment to obtain slurry with good fluidity and stability;
the aluminum oxide powder is prepared by mixing alpha-phase alumina with the average particle size of 3-5 mu m and alpha-phase alumina with the average particle size of 50nm according to a mass ratio of 40 to 60, the dispersant is prepared by compounding polyethyleneimine and sodium alkyl benzene sulfonate according to a mass ratio of 1:1-4:1, and the addition amounts of the solvent, the dispersant, the adhesive and the defoaming agent are 220%, 5.5%, 15% and 1.6% in sequence by taking the mass of the aluminum oxide powder as 100%;
(3) Tape casting and stamping: treating the slurry by a casting machine and a sheet punching machine to obtain a green compact sheet with a required shape and size;
(4) Rubber discharging: putting the green body sheet into a glue discharging furnace for discharging glue, wherein the specific technological parameters are as follows: performing first glue discharging in nitrogen atmosphere, heating to 580 ℃ at the heating rate of 2 ℃/min, preserving heat for 30min, performing second glue discharging in air atmosphere, heating to 240 ℃ at the heating rate of 4 ℃/min, and preserving heat for 100min;
(5) And (3) sintering: and (3) placing the green blank sheet after the glue removal into a sintering furnace, heating to 1500 ℃ at the speed of 2.5 ℃/min, preserving the heat for 20min, cooling to 1450 ℃, preserving the heat for 20h, and taking out after cooling to obtain the 996 aluminum oxide ceramic substrate.
The alumina ceramic substrate prepared in this example was tested and had the following properties: the relative density is 98.4 percent, and the volume density is 3.93g/cm 3 The bending strength was 509MPa.
Comparative example
The difference from example 1 is that: cuO-TiO 2 -SiO 2 The preparation method of the ternary sintering aid comprises the steps of weighing copper oxide, titanium dioxide and silicon dioxide in the same proportion as in example 1, putting the materials into a ball milling tank for ball milling for 24 hours, and then grinding and sieving to obtain CuO-TiO 2 -SiO 2 And (3) a ternary sintering aid.
The alumina ceramic substrate prepared by the comparative example is detected, and the performance is as follows: the relative density is 95.8 percent, and the volume density is 3.71g/cm 3 The bending strength was 420MPa.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (10)
1. A preparation method of a 996 alumina ceramic substrate is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a sintering aid: adding copper nitrate, titanium glycerol, tetraethoxysilane, acrylic acid, a polyethylenimine cross-linking agent, sodium tripolyphosphate and ethanol into a reactor filled with water in proportion, stirring for 30-60 min at the temperature of 60-70 ℃, then adding a free radical initiator, stirring for reaction until gel is formed, standing for 20-30 h at room temperature, then dehydrating and drying, grinding to obtain powder, then putting the powder into a calcining furnace for calcining to obtain CuO-TiO 2 -SiO 2 A ternary sintering aid;
(2) Preparation of slurry: adding alumina powder and a sintering aid into a ball mill according to a mass ratio of 99.6 to 0.4, simultaneously adding a solvent, a dispersing agent, a bonding agent and a defoaming agent into the ball mill, ball-milling for 15-20 h, and then feeding into a defoaming device for defoaming treatment to obtain slurry with good and stable fluidity;
the defoaming device comprises a defoaming tank and a vacuum pump, wherein a feed inlet and an air exhaust port are respectively arranged on two sides of the top of the defoaming tank, the air exhaust port is communicated with the vacuum pump through a vacuum tube, a driving motor is mounted on the top of the defoaming tank, the output end of the driving motor is fixedly connected with a rotating shaft, the bottom end of the rotating shaft penetrates through the top of the defoaming tank and is hinged with the top end of a stirring shaft, the stirring shaft is fixedly connected with the inner wall of the bottom of the defoaming tank through a bearing, the stirring shaft is fixedly connected with a plurality of first stirring units and second stirring units, the first stirring units and the second stirring units are alternately arranged along the length direction of the stirring shaft, the first stirring units comprise 3-6 stirring rods, the second stirring units comprise 2-4 stirring blades, the stirring rods and the outer walls of the stirring blades are fixedly connected with foam breaking burrs, the stirring rods comprise longitudinal stirring rods and transverse stirring rods, the longitudinal stirring rods and the transverse stirring rods are fixedly connected, a discharge port is arranged at the bottom of the side wall of the defoaming tank, and the discharge port is connected with a discharge pipe;
(3) Tape casting and stamping: after the slurry is processed by a casting machine and a sheet punching machine, a green compact sheet with the required shape and size is obtained;
(4) Rubber discharging: placing the green sheet into a glue discharging furnace for glue discharging;
(5) And (3) sintering: and placing the green blank sheet after the glue discharging into a sintering furnace, heating to 1500 ℃ at the speed of 1.5-2.5 ℃/min, preserving the heat for 10-20 min, cooling to 1450 ℃, preserving the heat for 12-20 h, cooling and taking out to obtain the 996 aluminum oxide ceramic substrate.
2. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the mass of the water in the step (1) is 100%, and the addition amount of each raw material component is as follows: 7 to 9 percent of copper nitrate, 16 to 20 percent of titanium glycerol, 36 to 42 percent of tetraethoxysilane, 8 to 12 percent of acrylic acid, 1 to 3 percent of polyethylenimine cross-linking agent, 0.2 to 0.4 percent of sodium tripolyphosphate, 8 to 15 percent of ethanol and 0.4 to 0.8 percent of free radical initiator.
3. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the free radical initiator is persulfate initiator.
4. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the calcining temperature in the step (1) is 620-660 ℃.
5. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the alumina powder is prepared by mixing alpha-phase alumina with the average grain size of 3-5 mu m and alpha-phase alumina with the average grain size of 50nm according to the mass ratio of 20-40.
6. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the dispersing agent is compounded by polyethyleneimine and sodium alkyl benzene sulfonate.
7. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: be equipped with deaeration portion between the discharging pipe, deaeration portion includes spherical shell and the dwang of setting in spherical shell, the vertical direction setting of dwang, the dwang outer wall has cup jointed the defoaming ball, be equipped with broken bubble thorn on the defoaming ball, when the dwang rotates under the drive arrangement effect, the drive takes off the bubble ball and rotates, eliminates remaining bubble in the thick liquids.
8. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the side wall of the defoaming tank is provided with a heating pipe, the heating pipe surrounds the defoaming tank, and the inner wall of the defoaming tank is provided with a temperature sensor.
9. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the addition amounts of the solvent, the dispersant, the adhesive and the defoaming agent are 180-220%, 3.5-5.5%, 10-15% and 0.9-1.6% in sequence based on 100% of the aluminum oxide powder by mass.
10. The method of claim 1, wherein the step of preparing the 996 alumina ceramic substrate comprises the steps of: the concrete process parameters of the glue discharging in the step (4) are as follows: performing first glue removal in a nitrogen atmosphere, heating to 500-580 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 30-50 min, then performing second glue removal in an air atmosphere, heating to 210-240 ℃ at a heating rate of 2-4 ℃/min, and preserving heat for 100-150 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732214A (en) * | 2012-06-20 | 2012-10-17 | 天津大学 | Ceramic corundum abrasive containing multiphase additive |
| CN109020514A (en) * | 2018-10-09 | 2018-12-18 | 揭阳市腾晟科技咨询有限公司 | A kind of preparation method of ceramic raw material |
| CN211328248U (en) * | 2019-11-22 | 2020-08-25 | 焦作市维纳科技有限公司 | Curtain coating thick liquids vacuum bubble removing device |
| CN215427452U (en) * | 2021-09-15 | 2022-01-07 | 江西永诚锂业科技有限公司 | Defoaming device for flotation beneficiation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732214A (en) * | 2012-06-20 | 2012-10-17 | 天津大学 | Ceramic corundum abrasive containing multiphase additive |
| CN109020514A (en) * | 2018-10-09 | 2018-12-18 | 揭阳市腾晟科技咨询有限公司 | A kind of preparation method of ceramic raw material |
| CN211328248U (en) * | 2019-11-22 | 2020-08-25 | 焦作市维纳科技有限公司 | Curtain coating thick liquids vacuum bubble removing device |
| CN215427452U (en) * | 2021-09-15 | 2022-01-07 | 江西永诚锂业科技有限公司 | Defoaming device for flotation beneficiation |
Non-Patent Citations (1)
| Title |
|---|
| 氧化铝陶瓷低温烧结助剂的研究进展;李悦彤等;《硅酸盐通报》;20111215(第06期);第108-112页 * |
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